KR20240008929A - Stable bis(alkyl-arene) transition metal complex and film deposition method using the same - Google Patents

Abstract

A method of forming a metal-containing film on a substrate is disclosed, comprising exposing the substrate to a vapor of a film forming composition containing a metal-containing precursor; and depositing at least a portion of the metal-containing precursor onto the substrate through a vapor deposition process to form the metal-containing film on the substrate, wherein the metal-containing precursor is pure M(alkyl-arene ) ₂ , where M is Cr, Mo or W; In arenes, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each selected from H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkylphenyl, C ₁ - independently _selected ^from C ₆ alkenylphenyl _, or _-SiXR ⁷ R ^{8 ,} wherein -C ₆ alkenyl.

Description

Stable bis(alkyl-arene) transition metal complex and film deposition method using the same

Cross-reference to related applications

This application is filed under 35 U.S.C. for U.S. patent application Ser. No. 17/327,045, filed May 21, 2021, the entire contents of which are incorporated herein by reference. Claims the benefit of priority under § 119 (a) and (b).

Technology field

The present invention relates to a transition metal-containing complex and a method of using the same to form a transition metal-containing film on a substrate by a vapor deposition process, specifically to a bis(alkyl-arene) transition metal complex and a transition metal-containing film using the same. It relates to a method of forming a film.

Molybdenum is a low-resistivity refractory metal used in microelectronic devices, for example as an alternative to tungsten. Molybdenum has a high melting point, high thermal conductivity, low coefficient of thermal expansion and low electrical resistivity. Molybdenum or molybdenum-containing films have been used, or have been proposed for use, as diffusion barriers, electrodes, photomasks, interconnects, or as low-resistivity gate structures. Molybdenum is a candidate to replace tungsten used in memory chips, logic chips, and other devices containing polysilicon-metal gate electrode structures. Thin films containing molybdenum may be used in some organic light-emitting diodes, liquid crystal displays, and thin-film solar cells and photovoltaic cells.

Gribov et al. (Doklady Akademii Nauk SSSR, Volume 194, Issue 3, Pages 580-582, 1970) described a film obtained by thermal decomposition at high temperature using M(arene) ₂ , in which the film contained some of carbon, pure Mo films were not obtained even at high temperatures. The films described were Cr(C ₆ H ₆ ) ₂ , Cr(MePh) ₂ , Cr(EtPh) ₂ , Cr(Me ₂ C ₆ H ₄ ) ₂ , bis(mesitylene)chromium, bis-(bis) on preheated samples. 10 ^-2 Torr from phenyl)chromium and their iodides, (aniline)-, (dimethylaniline)- and (mesitylene)tricarbonylchromium, (mesitylene)tricarbonylmolybdenum and bis(ethylbenzene)molybdenum. and deposited at 400 to 700°C.

Pure Mo films are desirable in the semiconductor industry. However, very few organometallic Mo containing complexes are available to form pure Mo films and have low impurity levels. For example, the commercial product Mo(Et-benzene) ₂ (US2019/0226086A) is available only as a mixture. The semiconductor industry needs to use complex products with high purity (at least >99%). US2019/0226086A claims the use of bis(alkyl-arene) molybdenum molecules for depositing Mo-containing films on substrates and only describes the use of Mo(Et-benzene) ₂ for depositing molybdenum carbide films. . Pure Mo films cannot be obtained due to the poor stability of the compound. Commercially available compounds are generally supplied as mixtures of isomers.

Metal arene complexes have been investigated as a source for the deposition of pure metallic films. For example, US2019/0226086, US20200115798 and US20190390340 disclose bis(alkyl-arene) molybdenum complex as a complex suitable for vapor phase deposition of molybdenum.

US 2019/0390340 by Yu et al. discloses a metal deposition method comprising forming a metal film by sequentially exposing a substrate to a metal precursor and an alkyl halide, wherein the metal precursor has a decomposition temperature higher than the deposition temperature, The alkyl halide comprises carbon and a halogen, the halogen comprises bromine or iodine, and the metal is selected from molybdenum, ruthenium, cobalt, copper, platinum, nickel or tungsten.

To obtain a product suitable for use as a semiconductor precursor, high purity and sufficient thermal stability are required under the desired conditions of use.

A method of forming a metal-containing film on a substrate is disclosed, comprising:

exposing the substrate to a vapor of a film forming composition containing a metal-containing precursor; and

Depositing at least a portion of the metal-containing precursor onto the substrate through a vapor deposition process to form the metal-containing film on the substrate.

Includes,

The metal-containing precursor is pure M(alkyl-arene) ₂ , where M is Cr, Mo or W;

Aren is

ego,

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkylphenyl, C ₁ - independently _selected ^from C ₆ alkenylphenyl _, or _-SiXR ⁷ R ^{8 ,} wherein -C ₆ alkenyl.

The disclosed method may include one or more of the following aspects:

● Pure M(alkyl-arene) ₂ precursors are Mo(toluene) ₂ , Mo(Et-benzene) ₂ , Mo( o -xylene) ₂ , Mo( m -xylene) ₂ , Mo( p -xylene) ₂ , Mo(mesitylene) ₂ , Mo(allyl-benzene) ₂ , Mo(1,3,5-Et ₃ -benzene) ₂ , Mo[(Me ₂ Si-Cl)-benzene] ₂ , Mo(styrene) ₂ , Mo(tetramethylsilane-benzene) ₂ , Mo[(4-vinylphenyl)benzene] ₂ , Mo(benzene)(Et-benzene), Mo(durene) ₂ , Mo(C ₆ H _5-2 ^H ) An aspect selected from ₂ ;

● Pure M(alkyl-arene) ₂ precursors are Cr(toluene) ₂ , Cr(Et-benzene) ₂ , Cr( o -xylene) ₂ , Cr( m -xylene) ₂ , Cr( p- xylene) ₂ , Cr (mesitylene) ₂ , Cr (allyl-benzene) ₂ , Cr (1,3,5-Et ₃ -benzene) ₂ , Cr[(Me ₂ Si-Cl)-benzene] ₂ , Cr (styrene) ₂ , Cr(tetramethylsilane-benzene) ₂ , Cr[(4-vinylphenyl)benzene] ₂ , Cr(benzene)(Et-benzene), Cr(durene) ₂ , Cr(C ₆ H ₅ - ² H) An aspect selected from ₂ ;

● Pure M(alkyl-arene) ₂ precursors are W(toluene) ₂ , W(Et-benzene) ₂ , W( o -xylene) ₂ , W( m -xylene) ₂ , W( p -xylene) ₂ , W (mesitylene) ₂ , W (allyl-benzene) ₂ , W (1,3,5-Et ₃ -benzene) ₂ , W[(Me ₂ Si-Cl)-benzene] ₂ , W (styrene) ₂ , W(tetramethylsilane-benzene) ₂ , W[(4-vinylphenyl)benzene] ₂ , W(benzene)(Et-benzene), W(durene) ₂ , or W(C ₆ H ₅ - ² H ) an aspect selected from ₂ ;

● Pure M(alkyl-arene) ₂ precursor is Mo( m -xylene) ₂ ;

● Pure M(alkyl-arene) ₂ precursor is Mo(toluene) ₂ ;

● Pure M(alkyl-arene) ₂ precursor is Mo(1,3,5-Et ₃ -benzene) ₂ ;

● Pure M(alkyl-arene) ₂ precursor is Mo(mesitylene) ₂ ;

● In embodiments where the pure M(alkyl-arene) ₂ precursor represents M(alkyl-arene) ₂ , the concentration of each of its isomers or any other impurity is less than about 15%, preferably less than about 10%, more preferably is less than about 5%, even more preferably less than about 1%;

● the film forming composition has a purity ranging from approximately 85% w/w to approximately 100% w/w;

● the film forming composition has a purity ranging from approximately 95% w/w to approximately 100% w/w;

● the film forming composition has a purity ranging from approximately 99% w/w to approximately 99.999% w/w;

● an embodiment in which the purity of the pure M(alkyl-arene) ₂ precursor ranges from approximately 85% w/w to approximately 100% w/w;

● an embodiment in which the purity of the pure M(alkyl-arene) ₂ precursor ranges from approximately 95% w/w to approximately 100% w/w;

● an embodiment in which the purity of the pure M(alkyl-arene) ₂ precursor ranges from approximately 99% w/w to approximately 99.999% w/w;

● an embodiment in which the purity of the pure M(alkyl-arene) ₂ precursor is greater than 85% w/w;

● The pure M(alkyl-arene) ₂ precursor has high thermal stability;

● The decomposition temperature of pure M(alkyl-arene) ₂ is approximately greater than 235°C;

● The decomposition temperature of pure M(alkyl-arene) ₂ is approximately greater than 240°C;

● the deposition temperature ranges from approximately 20° C. to approximately 600° C.;

● the deposition temperature ranges from approximately 20° C. to approximately 550° C.;

● the deposition temperature ranges from approximately 200° C. to approximately 600° C.;

● The deposition pressure ranges from vacuum to ambient pressure;

● The deposition pressure ranges from about 0.001 mTorr to about 760 Torr;

● The metal-containing film may be a pure metal, metal carbide, metal oxide, metal nitride, metal silicide film, or a combination thereof;

● An embodiment in which the metal-containing film is a pure metal film;

● An embodiment in which the metal-containing film is a metal carbide film;

● An embodiment in which the metal-containing film is a metal oxide film;

● An embodiment in which the metal-containing film is a metal nitride film;

● An embodiment in which the metal-containing film is a metal silicide film;

● An embodiment in which the metal-containing film is a molybdenum film;

● An embodiment in which the metal-containing film is a molybdenum carbide film;

● An embodiment in which the metal-containing film is a molybdenum oxide film;

● An embodiment in which the metal-containing film is a molybdenum nitride film;

● An embodiment in which the metal-containing film is a molybdenum silicide film;

● wherein the film forming composition comprises an inert carrier gas;

● The inert carrier gas is selected from N ₂ , He, Ne, Ar, Kr, Xe, or combinations thereof;

● The inert carrier gas is N ₂ or Ar;

● An aspect further comprising exposing the substrate to a co-reactant;

● An aspect further comprising the step of plasma treating the co-reactant;

● Co-reactants are SiH ₂ Cl ₂ , SiH ₂ I ₂ , SiHCl ₃ , SiCl ₄ , SiBr ₄ , Si ₂ Cl ₆ , Si ₂ Br ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ , CH ₂ I ₂ , CH ₃ I, C ₂ H ₅ I, C ₄ H ₉ I, or C ₆ H ₅ I, a halosilane, a polyhalodisilane (halo = F, Cl, Br, I), an organohalide;

● Co-reactants are selected from O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , N ₂ O, NO, NO ₂ , O· or OH· radicals, or mixtures thereof;

● Co-reactants are H ₂ , NH ₃ , N ₂ H ₄ , Me-N ₂ H ₄ , Me ₂ N ₂ H ₂ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , SiH ₂ Me ₂ , SiH ₂ Et ₂ , N(SiH ₃ ) ₃ , NH ₃ radical, H ₂ radical, or combinations thereof;

● Co-reactants are selected from NH ₃ , NO, N ₂ O, hydrazine, N ₂ plasma, N ₂ /H ₂ plasma, NH ₃ plasma, amines, and combinations thereof;

● The co-reactant is O ₂ ;

● The co-reactant is NH ₃ ;

● The co-reactant is H ₂ ;

● The vapor deposition process may be an ALD process, a CVD process, or a combination thereof;

● The vapor deposition process is an ALD process;

● The vapor deposition process is a CVD process;

● The vapor deposition process is a PEALD process;

● The substrate is selected from Si-containing substrates, metal substrates, metal-containing substrates or powder substrates;

● The substrate is a Si-containing substrate;

● The substrate is a metal substrate;

● The substrate is a metal-containing substrate;

● The substrate is a powder substrate;

● embodiments where the powder substrate comprises a non-limiting number of powder materials including NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate) and other battery cathode materials; and

● The powder substrate is activated carbon.

Notation and nomenclature

The following detailed description and claims generally use a number of abbreviations, symbols, and terms that are well known in the art. Certain abbreviations, symbols and terms are used throughout the following description and claims, including:

As used herein, singular refers to one or more.

As used herein, in the text or in the claims, “about, around” or “approximately” means ±10% of the stated value.

As used herein, in the text or in the claims, “room temperature” means approximately 20°C to approximately 25°C.

The term "pure" refers to a product in which the concentration of each of its isomers or any other impurity is less than about 15%, preferably less than about 10%, more preferably less than about 5%, and even more preferably less than about 1%. do.

The term "high thermal stability" means that no residue is produced above 200°C (more preferably residual amount is less than about 5% at 300°C, more preferably less than about 2% at 300°C), or "tail" a product that evaporates smoothly in thermogravimetric analysis without exhibiting " )", or a starting decomposition temperature that is higher than that of the commercially available product by DSC analysis, more preferably greater than 240°C. refers to

The term “substrate” refers to the material or materials on which the process is performed. A substrate may refer to a wafer having a material or materials on which a process is performed. The substrate may be any suitable wafer used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. The substrate may also have one or more layers of different materials already deposited on the substrate in previous manufacturing steps. For example, the wafer may include a silicon layer (e.g., crystalline, amorphous, porous, etc.), a silicon-containing layer (e.g., SiO ₂ , SiN, SiON, SiCOH, etc.), a metal-containing layer (e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel, ruthenium, gold, etc.), or a combination thereof. Additionally, the substrate may be planar or patterned. The substrate may be a patterned organic photoresist film. The substrate may be a dielectric material (e.g., ZrO ₂ -based material, HfO ₂ -based material, TiO ₂ -based material, rare earth oxide-based material, ternary oxide-based material, etc.) in MEMS, 3D NAND, MIM, DRAM, or FeRam device applications. It may include a layer of oxide used as an oxide layer or a nitride-based film (eg, TaN, TiN, NbN) used as an electrode. The substrate may also be a powder, such as a powder used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate) and other battery cathode materials. Exemplary powder substrates also include activated carbon.

The term “wafer” or “patterned wafer” refers to a wafer having a stack of films on a substrate, with at least the top film having topographic features created in steps prior to deposition of the indium-containing film.

The term “aspect ratio” refers to the ratio of the height of a trench (or opening) to the width of the trench (or diameter of the opening).

Note that, herein, the terms “film” and “layer” may be used interchangeably. It is understood that a film may correspond to or be associated with a layer, and that a layer may refer to a film. Additionally, those skilled in the art will recognize that the term "film" or "layer" as used herein refers to a piece of material of a certain thickness lying on or spread over a surface, which can be anywhere from as large as an entire wafer to as small as a trench or line. It will be recognized that the range may be up to. Throughout this specification and claims, the wafer and any associated layers on the wafer are referred to as the substrate.

Note that, herein, the terms “opening,” “via,” “hole,” and “trench” may be used interchangeably to refer to an opening formed in a semiconductor structure.

As used herein, the abbreviation “NAND” refers to a “Negative AND” or “Not AND” gate; The abbreviation “2D” refers to a two-dimensional gate structure on a planar substrate; The abbreviation “3D” refers to a three-dimensional or vertical gate structure, where the gate structures are stacked in a vertical direction.

Note that, herein, the terms “deposition temperature” and “substrate temperature” may be used interchangeably. It is understood that the substrate temperature may correspond to or be related to the deposition temperature, and the deposition temperature may refer to the substrate temperature.

Note that, herein, the terms “precursor” and “deposition compound” and “deposition gas” may be used interchangeably where the precursor is in a gaseous state at room temperature and ambient pressure. It is understood that a precursor may correspond to or be associated with a deposition compound or a deposition gas, and a deposition compound or deposition gas may refer to a precursor.

Standard abbreviations for elements from the Periodic Table of the Elements are used herein. Elements may be referred to by their abbreviations (e.g., Si refers to silicon, N refers to nitrogen, O refers to oxygen, C refers to carbon, H refers to hydrogen, , F refers to fluorine, etc.).

A unique CAS registration number (i.e., “CAS”) assigned by the Chemical Identification Service is provided to identify the specific molecule disclosed.

As used herein, the term “alkyl group” refers to a saturated functional group containing only carbon and hydrogen atoms. Alkyl groups are a type of hydrocarbon. Additionally, the term “alkyl group” refers to a linear, branched or cyclic alkyl group. Examples of linear alkyl groups include, without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyl groups include, without limitation, t-butyl. Examples of cyclic alkyl groups include, without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, and the like.

As used herein, the abbreviation “Me” refers to a methyl group; The abbreviation “Et” refers to an ethyl group; The abbreviation “Pr” refers to any propyl group (i.e., n-propyl or isopropyl); The abbreviation “ i Pr” refers to the isopropyl group; The abbreviation “Bu” refers to any butyl group ( n -butyl, iso -butyl, tert -butyl, sec -butyl); The abbreviation " t Bu" refers to the tert -butyl group; The abbreviation “ s Bu” refers to the sec -butyl group; The abbreviation " i Bu" refers to the iso -butyl group; The abbreviation “Ph” refers to the phenyl group; The abbreviation “Amy” refers to any amyl group ( iso -amyl, sec -amyl, tert -amyl); The abbreviation “Cy” refers to a cyclic hydrocarbon group (cyclobutyl, cyclopentyl, cyclohexyl, etc.); The abbreviation “Ar” refers to an aromatic hydrocarbon group (phenyl, xylyl, mesityl, etc.). As used in the disclosed embodiments, the term "independently" when used in a context describing an R group means that the subject R group is independently selected relative to another R group having the same or a different subscript or superscript, as well as a group of the same R group. It should be understood as indicating independent selection for any additional species. _For ^{example , in the formula} _MR ¹ There is no Additionally, unless specifically stated otherwise, the values of the R groups should be understood to be independent of each other when used in different chemical formulas.

As used herein, the abbreviation “ m- ” refers to “meta-”. For example, m -xylene refers to meta-xylene. The abbreviation " o -" refers to "ortho-". For example, o -xylene refers to ortho-xylene. The abbreviation " p- " refers to "para-". For example, p -xylene refers to para-xylene.

Ranges may be expressed herein as approximately from one particular value, and/or to approximately another particular value. When such ranges are expressed, alternative embodiments are to be understood as from one particular value and/or to another particular value, along with all combinations within the range. Any and all ranges recited in the disclosed embodiments include their endpoints regardless of whether the term “inclusively” is used (i.e., a range of x = 1 to 4 or 1 to 4 includes x = 1, x = 4, and x = any number in between).

Reference herein to “one embodiment” or “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places within the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments necessarily mutually exclusive of other embodiments. The same applies to the term “implementation”.

As used in this application, the word “exemplary” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over another aspect or design. Rather, the use of the word exemplary is intended to present the concept in a concrete way.

“Comprises” in a claim is an open transitional term, meaning that the elements of the previously identified claim are a non-exclusive list, i.e. any other may be additionally included and “comprises” "This means that it can be maintained within the range of “Comprising” is herein defined to include essentially the more limited linking terms “consisting essentially of” and “consisting of”; “Comprising” may therefore be replaced by “consisting essentially of” or “consisting of,” remaining within the scope of “comprising” as explicitly defined.

Additionally, the term “or” is intended to mean an inclusive “or” rather than an exclusive “or.” That is, unless otherwise specified or clear from context, “X utilizes A or B” is intended to mean any natural inclusive permutation. In other words, if X uses A, if X uses B, or if Additionally, as used in this application and the appended claims, the singular terms “a,” “an,” “an,” and “the,” or “an,” or “the,” or “an,” or “the,” or “an,” or “the,” or “an,” or “the,” or “the,” or “an,” or “the,” or “the,” or “the,” or “the,” or “the,” or “the,” or “the,” or “the,” or “one or more” is clearly intended to be clear from the context.

“Provide” within the claims is defined to mean to provide, supply, make available, or prepare something. A step may be performed by any act unless otherwise clearly stated in the claims to the contrary.

For a better understanding of the nature and purpose of the present invention, reference will be made to the following detailed description taken in conjunction with the accompanying drawings, in which like elements are assigned identical or similar reference numerals:
Figure 1 is the TGA of Mo(ethyl-benzene) ₂ ;
Figure 2 is a DSC of Mo(ethyl-benzene) ₂ ;
Figure 3 shows ⁹⁵ Mo NMR results for Mo(ethyl-benzene) ₂ ;
Figure 4 is an atmospheric TG analysis of Mo(mesitylene) ₂ ;
Figure 5 is DSC of Mo(mesitylene) ₂ ;
Figure 6 is an atmospheric TG analysis of Mo(1,3,5-Et ₃ -benzene) ₂ ;
Figure 7 is DSC of Mo(1,3,5-Et ₃ -benzene) ₂ ;
Figure 8 is an atmospheric TG analysis of Mo( m -xylene) ₂ ;
Figure 9 is DSC of Mo( m- xylene) ₂ ;
Figure 10 is an atmospheric TG analysis of Mo(toluene) ₂ ;
Figure 11 is DSC of Mo(toluene) ₂ ;
Figure 12 is an atomic profile of a film deposited by XPS of chemical vapor deposition of Mo( m- xylene) ₂ ;
Figure 13 is SEM data of pyrolytic deposition of Mo( m -xylene) ₂ ;
Figure 14 is an atomic profile of the deposited film by XPS of chemical vapor deposition of Mo( m- xylene) ₂ using H ₂ ;
Figure 15 is SEM data of chemical vapor deposition of Mo( m- xylene) ₂ using H ₂ .

A metal-containing film-forming composition comprising a bis(alkyl-arene) metal-containing precursor, M(alkyl-arene) ₂ (where M is Cr, Mo, W, etc.), and the use of the composition to produce semiconductors, photovoltaic cells, etc. A method for depositing metal-containing films using ALD, CVD, SOD, etc. for manufacturing, LCD-TFT, flat device, refractory materials or aerospace is disclosed. In particular, the present disclosure relates to CVD and ALD processes for the deposition of metal-containing films.

The disclosed metal-containing precursor can be pure M(alkyl-arene) ₂ , where M is Cr, Mo, or W;

Aren is

ego,

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkylphenyl, C ₁ - _{C 6} alkenylphenyl ^, _-SiXR ^{7 R 8} _, wherein C ₆ is selected from alkenyl.

In the context of “pure M(alkyl-arene) ₂ ,” the term “pure” means that the concentration of each of its isomers or any other impurity is less than about 15%, preferably less than about 10%, more preferably less than about 5%, or even more. More preferably it refers to less than about 1% product.

In one embodiment, the disclosed metal-containing film forming composition has less than 15% w/w, more preferably less than 10% w/w, and even more preferably less than 1% w/w of the minor isomer, reactant or other Contains any undesirable species, including reaction products, and may provide better process repeatability.

The purity of the disclosed metal-containing film forming composition is greater than 85% w/w (i.e., from 85.0% w/w to 100.0% w/w), preferably greater than 95% w/w (i.e., from 95.0% w/w to 100.0% w/w). 100.0% w/w), more preferably greater than 99% w/w (i.e., from 99.0% w/w to approximately 99.999% w/w or from 99.0% w/w to 100.0% w/w). Additionally, the purity of the disclosed metal-containing precursor, pure M(alkyl-arene) ₂ , is greater than 85% w/w (i.e., from 85.0% w/w to 100.0% w/w), preferably greater than 95% w/w. (i.e., from 95.0% w/w to 100.0% w/w), more preferably greater than 99% w/w (i.e., from 99.0% w/w to approximately 99.999% w/w or from 99.0% w/w to 100.0% w/w). Those skilled in the art will recognize that purity can be determined by gas or liquid chromatography and NMR spectroscopy in conjunction with mass spectrometry. The disclosed metal-containing film forming compositions may contain any of the following impurities: pyrazole; pyridine; Alkylamine; alkyl imine; THF; ether; pentane; cyclohexane; heptane; benzene; toluene; Chlorinated metal compounds; Lithium, sodium, potassium pyrazolyl. The total amount of these impurities is preferably less than 5% w/w (i.e., 0.0% w/w to 5.0% w/w), preferably less than 2% w/w (i.e., 0.0% w/w to 2.0% w/w), more preferably less than 1% w/w (i.e., 0.0% w/w to 1.0% w/w). The disclosed film forming compositions can be purified by recrystallization, sublimation, distillation, and/or passing the gaseous liquid through a suitable adsorbent such as 4Å molecular sieves.

The purification of the disclosed film forming compositions also independently removes metal impurities at levels ranging from 0 ppbw to 1 ppmw, preferably in the range of approximately 0 to approximately 500 parts per billion (ppbw), more preferably in the range of approximately 0 ppbw to approximately 100 ppbw. can be created. These metal or metalloid impurities include aluminum (Al), arsenic (As), barium (Ba), beryllium (Be), bismuth (Bi), cadmium (Cd), calcium (Ca), chromium (Cr), and cobalt (Co). ), copper (Cu), gallium (Ga), germanium (Ge), hafnium (Hf), zirconium (Zr), iron (Fe), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn) ), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), thorium (Th), tin (Sn), titanium (Ti), uranium (U), vanadium (V), and zinc (Zn). ) is included, but is not limited to this.

The disclosed M(alkyl-arene) ₂ precursors are Mo(toluene) ₂ , Mo(Et-benzene) ₂ , Mo( o- xylene) ₂ , Mo( m -xylene) ₂ , Mo( p -xylene) ₂ , Mo(mesitylene) ₂ , Mo(allyl-benzene) ₂ , Mo(1,3,5-Et ₃ -benzene) ₂ , Mo[(Me ₂ Si-Cl)-benzene] ₂ , Mo(styrene) ₂ , Mo(tetramethylsilane-benzene) ₂ , Mo[(4-vinylphenyl)benzene] ₂ , Mo(benzene)(Et-benzene), Mo(durene) ₂ , Mo(C ₆ H ₅ - ² H) ₂ , Cr (toluene) ₂ , Cr (Et-benzene) ₂ , Cr ( o -xylene) ₂ , Cr ( m -xylene) ₂ , Cr ( p -xylene) ₂ , Cr (mesitylene) ₂ , Cr (allyl-benzene) ₂ , Cr(1,3,5-Et ₃ -benzene) ₂ , Cr[(Me ₂ Si-Cl)-benzene] ₂ , Cr(styrene) ₂ , Cr(tetramethylsilane-benzene) ₂ , Cr[(4-vinylphenyl)benzene] ₂ , Cr(benzene)(Et-benzene), Cr(durene) ₂ , Cr(C ₆ H ₅ - ² H) ₂ , W(toluene) ₂ , W( Et-benzene) ₂ , W( o -xylene) ₂ , W( m -xylene) ₂ , W( p -xylene) ₂ , W(mesitylene) ₂ , W(allyl-benzene) ₂ , W( 1,3,5-Et ₃ -benzene) ₂ , W[(Me ₂ Si-Cl)-benzene] ₂ , W(styrene) ₂ , W(tetramethylsilane-benzene) ₂ , W[(4-vinylphenyl )benzene] ₂ , W (benzene) (Et-benzene), W (durene) ₂ , or W (C ₆ H ₅ - ² H) ₂ .

The disclosed metal-containing precursors can have high thermal stability and can be used to form high-speed, high-sensitivity semiconductor films, for example in CMOS systems, 3D NAND channels, or photodetectors. The disclosed metal-containing precursors and the disclosed film forming compositions are suitable for depositing corresponding element-containing films and are suitable for their related uses for depositing corresponding element-containing films. The disclosed films can be deposited uniformly on flat or patterned wafers, or in a “gap-fill” or “bottom-up gap-fill” approach.

Methods of using the metal-containing precursors disclosed for vapor deposition methods are also disclosed. The disclosed method provides the use of a metal-containing precursor to deposit a metal-containing film. The disclosed method may be useful in the fabrication of semiconductor, photovoltaic, LCD-TFT or flat panel devices. The disclosed method includes: providing a substrate; providing a vapor comprising at least one of the disclosed metal-containing precursors; exposing the substrate to a vapor of a film forming composition containing a metal-containing precursor; and depositing at least a portion of the metal-containing precursor onto the substrate through a vapor deposition process to form a metal-containing film.

A vapor of a metal-containing precursor is introduced into a reaction chamber containing at least one substrate. The temperature and pressure within the reaction chamber and the temperature of the substrate are maintained at conditions suitable for vapor deposition (e.g., ALD and CVD) of at least a portion of the metal-containing precursor onto the substrate. In other words, after introducing the vaporized precursor into the chamber, conditions within the chamber are adjusted such that at least a portion of the vaporized precursor is deposited onto the substrate to form a metal-containing film. Those skilled in the art will recognize that “at least a portion of the precursor is deposited” means that some or all of the precursor reacts with or adheres to the substrate. Herein, co-reactants may also be used to assist in the formation of metal-containing layers, as will be discussed later.

The reaction chamber can be any enclosure of the apparatus in which the deposition method is performed, such as, but not limited to, a parallel-plate reactor, cold-wall reactor, hot-wall reactor, single-wafer reactor, multi-wafer reactor, or other such types of deposition systems. Or it may be a chamber. All of these exemplary reaction chambers can serve as CVD or ALD reaction chambers. The reaction chamber may be maintained at a pressure ranging from vacuum to ambient pressure, for example, from about 0.001 mTorr to about 760 Torr. The pressure within the reaction chamber is the deposition pressure. Additionally, the temperature within the reaction chamber may range from about 20°C to about 600°C. Those skilled in the art will recognize that temperatures can be optimized through simple experimentation to achieve the desired results.

The temperature of the reactor can be controlled by controlling the temperature of the substrate holder or by controlling the temperature of the reactor walls. Devices used to heat the substrate are known in the art. The reactor walls are heated to a temperature sufficient to obtain the desired film with the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges to which the reactor walls can be heated include approximately 20°C to approximately 600°C. If a plasma deposition process is used, the deposition temperature may range from approximately 20°C to approximately 550°C. Alternatively, if a thermal process is performed, the deposition temperature may range from approximately 200°C to approximately 600°C.

Alternatively, the substrate can be heated to a temperature sufficient to obtain the desired metal-containing film having the desired physical state and composition at a sufficient growth rate. Non-limiting exemplary temperature ranges at which the substrate may be heated include 20°C to 600°C. Preferably, the temperature of the substrate is maintained below 500°C. Note that, herein, “deposition temperature” and “substrate temperature” may be used interchangeably. It is understood that the substrate temperature may correspond to or be related to the deposition temperature, and the deposition temperature may refer to the substrate temperature. When the reactor has reached thermal equilibrium, the temperature of the reactor wall can be equal to the deposition temperature and the substrate temperature.

The decomposition temperature of the disclosed metal-containing precursor is greater than approximately 235° C., more preferably greater than approximately 240° C., as can be seen from the examples below. The disclosed metal-containing precursor has high thermal stability. The term "high thermal stability" refers to a product that does not produce residuals above 200°C (more preferably residuals are less than about 5% at 300°C, more preferably less than about 2% at 300°C) or produces "tails". The product of M(alkyl-arene) ₂ evaporates smoothly in thermogravimetric analysis (TGA) without showing, or more preferably higher than the starting decomposition temperature of the commercially available product (approximately 235° C.) by DSC analysis. refers to the nature of the product M(alkyl-arene) ₂ which exhibits a starting decomposition temperature of approximately above 240°C.

The type of substrate on which the metal-containing film will be deposited may vary depending on the intended end use. In some embodiments, the substrate can be a patterned photoresist film made of hydrogenated carbon, such as CH _x , where x is greater than zero. In some embodiments, the substrate is an oxide (e.g., ZrO ₂ -based material, HfO ₂ -based material, TiO ₂ -based material, rare earth oxide-based material, ternary oxide-based material) used as a dielectric material in MIM, DRAM, or FeRam technologies. materials, etc.), or nitride-based films (e.g., TaN) used as oxygen barriers between copper and low-k layers. Other substrates can be used in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel devices. Examples of such substrates include solid substrates, such as metal nitride containing substrates (e.g., TaN, TiN, WN, TaCN, TiCN, TaSiN, and TiSiN); insulators (eg, SiO ₂ , Si ₃ N ₄ , SiON, HfO ₂ , Ta ₂ O ₅ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ and barium strontium titanate); or other substrates comprising any number of combinations of these materials. The actual substrate utilized may vary depending on the specific precursor embodiment utilized. However, in many cases, the preferred substrates utilized will be selected from hydrogenated carbon, TiN, strontium ruthenium oxide (SRO), Ru, and Si type substrates such as polysilicon or crystalline silicon substrates. The substrate may also be a powder, such as a powder used in rechargeable battery technology. A non-limiting number of powder materials include NMC (lithium nickel manganese cobalt oxide), LCO (lithium cobalt oxide), LFP (lithium iron phosphate) and other battery cathode materials. Exemplary powder substrates also include activated carbon.

The substrate may be patterned to include high aspect ratio vias or trenches. For example, conformal metal-containing films, such as SiO ₂ , can be formed on through silicon vias (TSVs) with aspect ratios ranging from approximately 20:1 to approximately 100:1 using any ALD technique. can be deposited on

The metal-containing film-forming composition may be used in pure form or in the form of toluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane, hexane, pentane, tertiary amine, acetone, tetrahydrofuran, ethanol, ethylmethylketone, 1 It can be supplied as a blend with a solvent suitable for vapor deposition, such as 4-dioxane. Alternatively, the metal-containing film forming composition may include a solvent suitable for casting deposition, such as naphtha, methylisobutylketone (MIBK), n-methylisobutylketone (NMIBK), or combinations thereof. Those skilled in the art will recognize that the casting deposition solution may further include pH adjusting agents or surfactants. The disclosed precursors can be present in various concentrations in solvent. For example, the final concentration of the vapor deposition solution may range from approximately 0.01 M to approximately 2 M. Those skilled in the art will recognize that the molarity of the casting deposition solution is directly proportional to the desired film thickness and the molarity can be adjusted accordingly.

For vapor deposition, pure or blended metal-containing precursors are introduced into the reactor in vapor form by conventional means such as tubing and/or flow meters. Precursors in vapor form can be obtained by vaporizing pure or blended precursor solutions through conventional vaporization steps, such as by direct vaporization, distillation, or bubbling, or by sublimation as disclosed in PCT Publication No. WO2009/087609 to Xu et al. It can be created using Pure or blended precursors may be fed to the vaporizer in liquid form, where they are vaporized prior to introduction into the reactor. Alternatively, pure or blended precursors can be vaporized by passing a carrier gas through a vessel containing the precursor or by bubbling the carrier gas into the precursor. The carrier gas may include, but is not limited to, N ₂ , He, Ne, Ar, Kr, Xe, and mixtures thereof. Bubbling with a carrier gas may remove any dissolved oxygen present in the pure or blended precursor solution. The carrier gas and precursor are then introduced into the reactor as vapors.

If desired, the vessel containing the disclosed film forming composition can be heated to a temperature at which the metal-containing precursor is in the liquid phase and has sufficient vapor pressure. The container may be maintained at a temperature ranging from approximately 0° C. to approximately 150° C., for example. Those skilled in the art will recognize that the temperature of the vessel can be adjusted in known ways to control the amount of metal-containing precursor vaporized.

The reactor may be, but is not limited to, parallel-plate reactors, cold-wall reactors, hot-wall reactors, single-wafer reactors, multi-wafer reactors, and other types of deposition systems under suitable conditions that allow the compounds to react to form layers. , may be any enclosure chamber within the device in which the deposition method is performed. Those skilled in the art will recognize that any of these reactors can be used in either ALD or CVD deposition processes.

In addition to the disclosed metal-containing precursors, co-reactants can be introduced into the reactor to form metal-containing films. When the target deposited film is a dielectric film, the co-reactants are oxidizing gases such as O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , NO, N ₂ O, NO ₂ , oxygen-containing radicals such as O· or OH·. ; NO; NO ₂ ; Alcohols, silanols, aminoalcohols, carboxylic acids such as formic acid, acetic acid, propionic acid; NO, NO ₂ or radical species of carboxylic acids; para-formaldehyde; and mixtures thereof. Preferably, the oxidizing agent is from the group consisting of O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , N ₂ O, NO, NO ₂ , oxygen-containing radicals thereof such as O· or OH·, or mixtures thereof. is selected from Preferably, when an ALD process is performed, the co-reactant is plasma treated oxygen, ozone, or a combination thereof. If an oxidizing gas is used as a co-reactant, the resulting metal-containing film will also contain oxygen.

Alternatively, when the target is a conductive film, the co-reactants include reducing agents such as H ₂ , NH ₃ , (SiH ₃ ) ₃ N, hydridosilanes (such as SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H ₁₀ , Si ₆ H ₁₂ ), chlorosilanes and chloropolysilanes (e.g. SiHCl ₃ , SiH ₂ Cl ₂ , SIH ₃ Cl, Si ₂ Cl ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ ), alkylsilanes (eg, (CH ₃ ) ₂ SiH ₂ , (C ₂ H ₅ ) ₂ SiH ₂ , (CH ₃ )SiH ₃ , (C ₂ H ₅ )SiH ₃ ), hydrazine (eg, N ₂ H ₄ , MeHNNH ₂ , MeHNNHMe), organic amines (e.g. N(CH ₃ )H ₂ , N(C ₂ H ₅ )H ₂ , N(CH ₃ ) ₂ H, N(C ₂ H ₅ ) ₂ H, N( CH ₃ ) ₃ , N(C ₂ H ₅ ) ₃ , (SiMe ₃ ) ₂ NH), pyrazoline, pyridine, B-containing molecules (e.g. B ₂ H ₆ , 9-borabicyclo[3,3,1 ]nonane, trimethylboron, triethylboron, borazine), an alkyl metal (e.g., trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc), radical species thereof, and mixtures thereof. Co-reactants may be primary amines, secondary amines, tertiary amines, trisilylamines, radicals thereof, and mixtures thereof. Preferably, the reducing agent is H ₂ , NH ₃ , N ₂ H ₄ , Me-N ₂ H ₄ , Me ₂ N ₂ H ₂ , SiH ₄ , Si ₂ H ₆ , Si 3 H ₈ , _{Si 4 H 10} , SiH ₂ Me ₂ , SiH ₂ Et ₂ , N(SiH ₃ ) ₃ , NH ₃ radical, H ₂ radical, or a combination thereof. When a reducing agent is used, the resulting metal-containing film may be a pure metal, metal carbide, metal oxide, metal nitride, metal silicide film, or a combination thereof. If an N-containing reducing agent is used, the resulting metal-containing film will also contain nitrogen.

Additionally, co-reactants may be halosilanes, polyhalodisilanes (halo = F, Cl, Br, I), or organic halides such as SiH ₂ Cl ₂ , SiH ₂ I ₂ , SiHCl ₃ , SiCl ₄ , SiBr ₄ , Si ₂ Cl ₆ , Si ₂ Br ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ , CH ₂ I ₂ , CH ₃ I, C ₂ H ₅ I, C ₄ H ₉ I, C ₆ H ₅ I, and metal-containing It may be one or more reactant gases that form a film, such as a pure metal, and a metal carbide film. Halide-containing co-reactants such as CH ₂ I ₂ , CH ₃ I, C ₂ H ₅ I, C ₄ H ₉ I, C ₆ H ₅ I are used to catalyze product decomposition and obtain gap filling or bottom-up gap filling. It's helpful.

Additionally, the co-reactants can be treated by plasma to decompose the reaction gas into radical form, and at least one of H ₂ , N ₂ and O ₂ is used as a hydrogen, nitrogen or oxygen source gas, respectively, when treated with plasma. It can be. The plasma source is N ₂ plasma, N ₂ /He plasma, N ₂ /Ar plasma, NH ₃ plasma, NH ₃ /He plasma, NH ₂ /Ar plasma, He plasma, Ar plasma, H ₂ plasma, H ₂ /He plasma. , H ₂ /organic amine plasma, and mixtures thereof. N ₂ can also be used as a reducing agent when treated with plasma. For example, the plasma may be generated at a power ranging from about 50 W to about 500 W, preferably from about 100 W to about 200 W. The plasma may exist within or be generated within the reactor itself. Alternatively, the plasma may be at a location that is generally removed from the reactor, such as a remote location plasma system. Those skilled in the art will recognize suitable methods and devices for such plasma processing.

For example, co-reactants can be introduced directly into a plasma reactor that generates a plasma in the reaction chamber to produce plasma-treated reactants in the reaction chamber. Co-reactants may be introduced and maintained within the reaction chamber prior to plasma treatment. Alternatively, plasma treatment can occur simultaneously with introduction of the reactants.

Alternatively, the plasma-treated co-reactants can be generated outside the reaction chamber, for example, as a remote plasma to treat the co-reactants before entering the reaction chamber.

A method of forming a metal-containing layer on a substrate using a vapor deposition process is also disclosed. Applicants believe that the disclosed film forming compositions are suitable for ALD. More specifically, the disclosed film forming compositions provide surface saturation, self-limiting growth from cycle to cycle, and aspect ratios ranging from approximately 2:1 to approximately 200:1, and preferably from approximately 60:1 to approximately 150:1. Perfect step coverage is possible. Additionally, the disclosed film-forming compositions have high decomposition temperatures and thus exhibit good thermal stability to enable ALD. High decomposition temperatures enable ALD at higher temperatures, producing films with higher purity.

The disclosed metal-containing precursor and one or more co-reactants may be introduced into the reaction chamber simultaneously (CVD), sequentially (ALD), or in other combinations. For example, the disclosed metal-containing precursor can be introduced in one pulse, and two additional metal sources can be introduced together in separate pulses (modified atomic layer deposition). Alternatively, the reaction chamber may already contain reactants prior to introduction of the metal-containing precursor. Reactants may pass through the plasma system, either localized or remote from the reaction chamber, and decompose into radicals. Alternatively, the metal-containing precursor can be introduced continuously into the reaction chamber while the other metal source is introduced by pulses (pulse-CVD). In each example, the pulse may be followed by a purge or evacuation step to remove excess introduced components. In each example, the pulse may last for a period of about 0.01 seconds to about 10 seconds, alternatively about 0.3 seconds to about 3 seconds, alternatively about 0.5 seconds to about 2 seconds. In another alternative, the metal-containing precursor and one or more reactants can be sprayed simultaneously from a shower head, under which a susceptor supporting several wafers is rotated (spatial ALD).

The disclosed film forming compositions can be used to deposit metal-containing films using any deposition method known to those skilled in the art. Examples of suitable deposition methods include CVD or ALD, with or without plasma enhanced. More specifically, exemplary suitable deposition methods include, but are not limited to, thermal ALD, plasma-enhanced ALD (PEALD), space-partitioned ALD, temporal ALD, selective or non-selective ALD, hot-wire ALD (HWALD), radical-incorporated ALD, and combinations thereof. This is included. To provide adequate step coverage and film thickness control, the deposition method is preferably ALD, PE-ALD or spatial ALD. Exemplary CVD methods include metal-organic CVD (MOCVD), thermal CVD, pulsed CVD (PCVD), low pressure CVD (LPCVD), subatmospheric pressure CVD (SACVD) or atmospheric pressure CVD (APCVD), hot wire CVD, or hot filament CVD (cat- Also known as CVD (where a hot wire is used as the energy source for the deposition process), hot wall CVD, cold wall CVD, aerosol-assisted CVD, direct liquid injection CVD, combustion CVD, hybrid physical CVD, metal-organic CVD, fast thermal CVD, optical -initiated CVD, laser CVD, radical-incorporated CVD, plasma-enhanced CVD (PECVD) (including but not limited to flowable PECVD), and combinations thereof.

In one non-limiting example ALD-type process, a vapor phase of a metal-containing precursor is introduced into a reaction chamber, where it is contacted with a suitable substrate. Excess metal-containing precursor may then be removed from the reaction chamber by purging and/or evacuation of the reaction chamber. An oxygen source is introduced into the reaction chamber, where it reacts in a self-limiting manner with the absorbed metal-containing precursor. Any excess oxygen source is removed from the reaction chamber by purging and evacuating the reaction chamber. If the desired film is a metal oxide film, this two-step process can be repeated to provide the desired film thickness or until a film with the required thickness is obtained.

As another alternative, the metal-containing film can be deposited by the flowable PECVD method disclosed in US Patent Application Publication No. 2014/0051264 using the disclosed metal-containing precursor and radical nitrogen- or oxygen-containing co-reactant. Radical nitrogen- or oxygen-containing co-reactants, such as NH ₃ or H ₂ O, respectively, are produced in the remote plasma system. The vapor phases of the radical co-reactant and the initiated precursor are introduced into a reaction chamber, where they react to deposit an initially flowable film on the substrate. Applicants believe that the nitrogen atoms of the disclosed compounds help further improve the flowability of the deposited film, resulting in a film with fewer voids.

Also disclosed are methods using metal-containing precursors disclosed in casting deposition methods, such as spin coating (i.e., SOD), spray coating, dip coating, or slit coating techniques. The disclosed method provides for the use of a metal-containing film forming composition to deposit a metal-containing film. The disclosed method includes: providing a substrate; Applying a liquid form of the disclosed metal-containing film forming composition containing the disclosed metal-containing precursor onto a substrate; and forming a metal-containing layer on the substrate. As discussed above, the liquid form of the disclosed metal-containing film forming composition may be a pure solution of the metal-containing precursor, or a mixture of the metal-containing precursor with a solvent and an optional pH adjuster or surfactant. In one embodiment, the metal-containing film forming composition may be supplied in a blend with a solvent suitable for SOD, for example, the metal-containing film forming composition may include toluene, ethyl benzene, xylene, mesitylene, decane, dode. Can be mixed with kan, octane, hexane, pentane, tertiary amine, acetone, tetrahydrofuran, ethanol, ethylmethylketone or 1,4-dioxane to form a liquid form of the metal-containing film forming composition for SOD. .

The liquid form of the disclosed metal-containing film forming composition can be applied directly to the center of the substrate or can be applied over the entire substrate by spraying. When applied directly to the center of the substrate, the substrate can be rotated to utilize centrifugal force to distribute the composition evenly over the substrate. Alternatively, the substrate can be dipped into the metal-containing film forming composition. The resulting film can be dried at an appropriate temperature for a period of time to vaporize any solvent or volatile components of the film. Those skilled in the art will recognize that the appropriate temperature is selected based on the solvent to be evaporated. During the vaporization process, a mist of water may be sprayed onto the substrate to promote the hydrolysis reaction of the film.

Once the desired film thickness is achieved, the film can be subjected to additional processes such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure. . Those skilled in the art will recognize the systems and methods used to perform these additional processing steps. For example, the metal-containing film can be heated under an inert atmosphere, an H-containing atmosphere, an N-containing atmosphere, an O-containing atmosphere, or a combination thereof, at a temperature ranging from approximately 200° C. to approximately 1000° C. for a period of from approximately 0.1 seconds to approximately 7200 seconds. Exposure may occur for a range of times. Most preferably, the temperature is 600° C. for less than 3600 seconds in an H-containing atmosphere. The resulting film may contain fewer impurities and therefore may have improved performance characteristics. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate can be removed from the reaction chamber and the annealing/flash annealing process is performed in a separate apparatus. Although any of the above post-treatment methods have been found to be effective in reducing carbon and nitrogen contamination of metal-containing films, thermal annealing has been found to be particularly effective.

Example

The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all-inclusive, nor are they intended to limit the scope of the invention described herein.

Thermogravimetric (TG) analysis was performed at 25°C to 500°C under atmospheric pressure (1000 mBar, N ₂ 220 sccm) or vacuum (20 mBar, N ₂ 20 sccm) in an aluminum open cup. Vapor pressure (VP) was determined by TG analysis from 60°C to 180°C using naphthalene as an external standard. Differential scanning calorimetry (DSC) was measured with Au-coated sealed pans up to 300°C or 400°C.

The bis(alkyl-arene)metal complex was prepared by reported methods (VS Asirvatham et al. Organometallics 2001 , 20 , 1687-1688; L. Calucci et al. Dalton Trans. 2006 , 4228-4234).

Comparative Example 1 - Thermal properties of pure Mo(ethyl-benzene) ₂ versus commercially available Mo(ethyl-benzene) ₂

Figure 4 is a TG analysis of Mo(mesitylene) ₂ in air. This shows that Mo(mesitylene) ₂ evaporates without decomposition under these conditions. The vapor pressure of the compound is 1 Torr at 143°C. DSC results for Mo(mesitylene) ₂ ( Figure 5 ) show a melting point at approximately 105°C and a decomposition point at 248°C. The results are compared with other compounds in Table 1 below.

Example 2 - Thermal properties of pure Mo(1,3,5-Et ₃ -benzene) ₂

The obtained molecule is oil at ambient temperature. Figure 6 is an atmospheric TG analysis of Mo(1,3,5-Et ₃ -benzene) ₂ . This shows that Mo(1,3,5-Et ₃ -benzene) ₂ evaporates without decomposition under these conditions. The vapor pressure of the compound is 1 Torr at 151°C. DSC results of Mo(1,3,5-Et ₃ -benzene) ₂ ( FIG. 7 ) show a decomposition point at 246°C. The results are compared with other compounds in Table 1 below.

Example 3 - Thermal properties of pure Mo( m -xylene) ₂

Figure 8 shows the atmospheric TG analysis of Mo(m-xylene) ₂ . This shows that Mo(m-xylene) ₂ evaporates without decomposition under these conditions. The vapor pressure of the compound is 1 Torr at 130℃. DSC results for Mo(m-xylene) ₂ ( Figure 9 ) show a melting point at approximately 110°C and a decomposition point at 280°C. The results are compared with other compounds in Table 1 below.

Example 4 - Thermal properties of pure Mo(toluene) ₂

Figure 10 is a TG analysis of Mo(toluene) ₂ in air. The vapor pressure of the compound is 1 Torr at 133°C. DSC results of Mo(toluene) ₂ ( Figure 11 ) show a melting point at 72°C and a decomposition point at 252°C. The results are compared with other compounds in Table 1 below.

[Table 1]

Example 5 - Deposition of Mo-containing films by Mo( m -xylene) ₂ without co-reactants

Mo( m- xylene) ₂ was heated at 120° C., and its vapor was provided to the reaction chamber by supplying 150 sccm Ar for 30 minutes. At this time, the chamber was heated to 420°C. The obtained film was analyzed by XPS and SEM. This indicated that the deposited film had Mo and C in the film and had a thickness of 25.9 to 31 nm. Figure 12 is the atomic profile of the deposited film by XPS of chemical vapor deposition of Mo( m- xylene) ₂ (squares: molybdenum, triangles: carbon, filled circles: oxygen, and empty circles: silicon). Figure 13 is SEM data of pyrolytic deposition of Mo( m -xylene) ₂ .

Example 6 - Deposition of Mo-containing films by Mo( m- xylene) ₂ using H ₂ as co-reactant

Mo( m- xylene) ₂ was heated at 120° C., and its vapor was provided to the reaction chamber by supplying 150 sccm Ar for 30 minutes. The chamber was heated at 420° C., and 50 sccm of H ₂ as a co-reactant was provided to the reaction chamber. The obtained film was analyzed by XPS and SEM. This indicated that the deposited film had Mo and C in the film and had a thickness of 84.7 to 84.8 nm. Figure 14 is the atomic profile of the deposited film by XPS of chemical vapor deposition of Mo( m- xylene) ₂ using H ₂ (squares: molybdenum, triangles: carbon, filled circles: oxygen, and empty circles: silicon) ). Figure 15 is SEM data of chemical vapor deposition of Mo( m- xylene) ₂ using H ₂ .

Predictive Example 1 - Pure Mo film obtained using Mo(alkyl-arene) ₂

More pure or less contaminated Mo films can be obtained when co-reactants such as hydrogen, other reducing agents, other co-reactants, or combinations thereof are used at deposition temperatures in the range of 200°C to 400°C. Exemplary Mo(alkyl-arene) ₂ include Mo( m -xylene) ₂ , Mo(toluene) ₂ , Mo(1,3,5-Et ₃ -benzene) ₂ , Mo(mesitylene) ₂ , Mo(ethyl) -benzene) ₂ is included.

Predictive Example 2 - Pure W film obtained using W(alkyl-arene) ₂

Pure W(alkyl-arene) ₂ was synthesized according to the reported synthetic route. When using these molecules in a CVD manner, it is expected that pure W films can be obtained when co-reactants such as hydrogen or other reducing agents are used at deposition temperatures in the range of 200°C to 400°C. Exemplary W(alkyl-arene) ₂ include W( m -xylene) ₂ , W(toluene) ₂ , W(1,3,5-Et ₃ -benzene) ₂ , W(mesitylene) ₂ , W(ethyl) -benzene) ₂ is included.

Predictive Example 3 - Pure Cr film obtained using Cr(alkyl-arene) ₂

Pure Cr(alkyl-arene) ₂ was synthesized according to the reported synthetic route. When using these molecules in a CVD manner, it is expected that pure W films can be obtained when co-reactants such as hydrogen or other reducing agents are used at deposition temperatures in the range of 200°C to 400°C. Exemplary Cr(alkyl-arene) ₂ include Cr( m -xylene) ₂ , Cr(toluene) ₂ , Cr(1,3,5-Et ₃ -benzene) ₂ , Cr(mesitylene) ₂ , Cr(ethyl) -benzene) ₂ is included.

Although the claimed subject matter described herein may be described with respect to example implementations for processing one or more computing application features/operations for computing applications with user-interaction components, the claimed subject matter is limited to such specific embodiments. It doesn't work. Rather, the techniques described herein may be applied to any suitable type of user-interactive component execution management method, system, platform and/or device.

Numerous further modifications of the details, materials, steps, and arrangements of parts described and illustrated herein for the purpose of explaining the essence of the invention may be made by those skilled in the art within the spirit and scope of the invention as set forth in the appended claims. You will understand that it can be done. Accordingly, the present invention is not limited to the specific embodiments of the above-described embodiments and/or the accompanying drawings.

Although embodiments of the invention have been presented and described, modifications may be made by those skilled in the art without departing from the spirit or teachings of the invention. The embodiments described herein are illustrative only and not limiting. Many variations and modifications of the compositions and methods are possible and are within the scope of the present invention. Accordingly, the scope of protection is not limited to the embodiments described herein, but is limited only by the following claims, which scope includes all equivalents to the subject matter of the claims.

Claims (15)

A method of forming a metal-containing film on a substrate, comprising:
exposing the substrate to a vapor of a film forming composition containing a metal-containing precursor; and
Depositing at least a portion of the metal-containing precursor onto the substrate through a vapor deposition process to form the metal-containing film on the substrate.
Includes,
The metal-containing precursor is a pure M(alkyl-arene) ₂ precursor, where M is Cr, Mo, or W;
Aren is
ego,
In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkylphenyl, C ₁ - independently _selected ^from C ₆ alkenylphenyl _, or _-SiXR ⁷ R ^{8 ,} wherein -C ₆ alkenyl. According to paragraph 1,
The pure M (alkyl-arene) ₂ precursor is Mo (toluene) ₂ , Mo (Et-benzene) ₂ , Mo ( o -xylene) ₂ , Mo ( m -xylene) ₂ , Mo( p -xylene) ₂ , Mo(mesitylene) ₂ , Mo(allyl-benzene) ₂ , Mo(1,3,5-Et ₃ -benzene) ₂ , Mo[(Me ₂ Si-Cl)-benzene] ₂ , Mo(styrene) ₂ , Mo(tetramethylsilane-benzene) ₂ , Mo[(4-vinylphenyl)benzene] ₂ , Mo(benzene)(Et-benzene), Mo(durene) ₂ , Mo(C ₆ H _5-2 ^H ) ₂ , Cr (toluene) ₂ , Cr (Et-benzene) ₂ , Cr ( o -xylene) ₂ , Cr ( m -xylene) ₂ , Cr ( p -xylene) ₂ , Cr (mesitylene) ₂ , Cr(allyl-benzene) ₂ , Cr(1,3,5-Et ₃ -benzene) ₂ , Cr[(Me ₂ Si-Cl)-benzene] ₂ , Cr(styrene) ₂ , Cr(tetramethylsilane-benzene ) ₂ , Cr[(4-vinylphenyl)benzene] ₂ , Cr(benzene)(Et-benzene), Cr(durene) ₂ , Cr(C ₆ H ₅ - ² H) ₂ , W(toluene) ₂ , W (Et-benzene) ₂ , W( o -xylene) ₂ , W( m -xylene) ₂ , W( p -xylene) ₂ , W(mesitylene) ₂ , W(allyl-benzene) ₂ , W (1,3,5-Et ₃ -benzene) ₂ , W[(Me ₂ Si-Cl)-benzene] ₂ , W(styrene) ₂ , W(tetramethylsilane-benzene) ₂ , W[(4-vinyl phenyl)benzene] ₂ , W(benzene)(Et-benzene), W(durene) ₂ , or W(C ₆ H ₅ - ² H) ₂ . According to paragraph 1,
The M(alkyl-arene) ₂ precursor is Mo( m -xylene) ₂ , method. According to paragraph 1,
The M(alkyl-arene) ₂ precursor is Mo(toluene) ₂ , method. According to paragraph 1,
The M(alkyl-arene) ₂ precursor is Mo(1,3,5-Et ₃ -benzene) ₂ , method. According to paragraph 1,
The M(alkyl-arene) ₂ precursor is Mo(mesitylene) ₂ , method. According to paragraph 1,
The purity of the pure M(alkyl-arene) ₂ precursor is greater than 85% w/w. According to paragraph 1,
The method of claim 1 , wherein the decomposition temperature of the pure M(alkyl-arene) ₂ precursor is greater than approximately 240°C. In clause 1,
The method of claim 1 , wherein the film forming composition comprises an inert carrier gas selected from N ₂ , He, Ne, Ar, Kr, Xe, or combinations thereof. According to paragraph 1,
The method further comprising exposing the substrate to a co-reactant. According to any one of claims 1 to 10,
The method further comprising plasma treating the co-reactant. According to any one of claims 1 to 10,
The co-reactants are SiH ₂ Cl ₂ , SiH ₂ I ₂ , SiHCl ₃ , SiCl ₄ , SiBr ₄ , Si ₂ Cl ₆ , Si ₂ Br ₆ , Si ₂ HCl ₅ , Si ₃ Cl ₈ , CH ₂ I ₂ , CH ₃ I, a halosilane selected from C ₂ H ₅ I, C ₄ H ₉ I or C ₆ H ₅ I, a polyhalodisilane (halo = F, Cl, Br, I), an organohalide. According to any one of claims 1 to 10,
The method of claim 1 , wherein the co-reactant is selected from O ₂ , O ₃ , H ₂ O, H ₂ O ₂ , N ₂ O, NO, NO ₂ , O · or OH · radicals, or mixtures thereof. According to any one of claims 1 to 10,
The co-reactants are H ₂ , NH ₃ , N ₂ H ₄ , Me-N ₂ H ₄ , Me ₂ N ₂ H ₂ , SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , SiH ₂ Me. ₂ , SiH ₂ Et ₂ , N(SiH ₃ ) ₃ , NH ₃ radical, H ₂ radical, or combinations thereof. According to any one of claims 1 to 10,
The method of claim 1, wherein the co-reactant is selected from NH ₃ , NO, N ₂ O, hydrazine, N ₂ plasma, N ₂ /H ₂ plasma, NH ₃ plasma, amines, and combinations thereof.